A kind of can the nanofiber of increasing specific surface area
Technical field
The present invention relates to a kind of can the nanofiber of increasing specific surface area.
Background technology
Electrostatic spinning technique is realized in 1934 by Formhals etc. the earliest. From eighties of last century eighties particularly recently for over ten years (about before and after nineteen ninety-five), promotion by Nano-technology Development upsurge, Static Spinning receives publicity again, utilize this technology, it is easy to many Polymer Processing are become the superfine fibre of different fibre structures, different scale (submicron to nanometer).
The polymer nanofiber that electrostatic spinning technique has successfully been prepared is utilized to include poly-phthalein amine (PA6, PA66), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polylactic acid (PLA), cellulose acetate (CA), polyurethane (PU), many polymeric matrixs such as PC (PCL). Acrylonitrile copolymer is dissolved in solvent by Chinese patent " preparation method and application of a kind of affinity vinyl cyanide base co-polymer superfine fibre film " (publication number CNl01185851), carry out electrostatic spinning, preparing a kind of affinity vinyl cyanide co-polymer superfine fibre film, fibre diameter is 80-800run. United States Patent (USP) Electrospunelectroactivepolymers (publication number 20060057377) is by the polymer with polar group, it is dissolved in solvent such as polyamide, polyurethane, polyacrylic acid etc., carry out electrostatic spinning, having prepared the polymer nanofiber with electrical conductive activities, fibre diameter is 10-10000nm. It polymer nanofiber-based prepared currently with method of electrostatic spinning is the room temperature polymeric matrix that is in glassy state or crystalline state, because after the macromole of these polymer is ejected fiber by super drawing under electrostatic induction, can again be changed into glassy state or crystalline state rapidly and be fixed up in the quick volatilization process of solvent or in fast cooling cooling procedure, fiber is indeformable, it is easy to control the stability of spinning process.
Titanium dioxide; it is commonly called as titanium dioxide; of light color; stable in properties, has the performance of good covering power and quasiconductor, and valuable especially is that titanium white is nontoxic; inexpensive; raw material sources are extensive, and use cost is low, is applied to the aspects such as rubber industry, plastics industry, paper industry, coatings industry, daily use chemicals and medical industry, food industry, environmental conservation more.
ATO, Chinese name tin-antiomony oxide, there is good light transmission and electric conductivity, excellent thermal insulation powder, conducting powder (antistatic powder) use, its good heat-proof quality can be made, be widely used in the fields such as coating, chemical fibre, polymeric membrane; As conductive material, dispersibility, resistance to activity, thermoplasticity, wearability, safety have the advantage that other conductive materials (such as graphite, surfactant, metal powder etc.) are incomparable, it is applied to the aspects such as photoelectric display device, transparency electrode, solaode, liquid crystal display, catalysis more, but ATO is expensive, use cost is higher, and powder body is navy blue, limit its application to a certain extent.
TiO2With the preparation of ATO composite, meet the material requirement to color, reduce the cost of conductive material, improve the using value of material. And TiO2The preparation present stage research of/ATO composite is less, in the related data found, have employed chemical coprecipitation method, by TiO more2Surface coating ATO prepares conductive powder body, and products application has certain limitation.
Summary of the invention
The present invention devise a kind of can the nanofiber of increasing specific surface area, it solves the technical problem that it is that existing nanofiber does not have great specific surface area, is simultaneously fabricated into high.
In order to solve the technical problem of above-mentioned existence, present invention employs below scheme:
A kind of can the nanofiber of increasing specific surface area, this high surface area nanofibers is nucleocapsid structure, and its stratum nucleare is titanium dioxide (TiO2), shell is tin-antiomony oxide (ATO), and shell tin-antiomony oxide (ATO) is SnO2Middle doping Sb element, wherein the weight/mass percentage composition of Sb element is 2O-80%, and fibre structure is the nucleocapsid structure of tin-antiomony oxide cladding titanium dioxide, wherein TiO2Weight/mass percentage composition be 20-80%, the weight/mass percentage composition of ATO is 20-80%, the nanofiber average diameter of nucleocapsid structure is 100-450nm, it is characterised in that: step 1, butyl titanate and polyvinylpyrrolidone being dissolved in ethanol, stirring obtains homogeneous stratum nucleare spinning liquid; Step 2, being dissolved in DMF by stannic chloride pentahydrate, Butter of antimony., polyvinylpyrrolidone, stirring obtains homogeneous shell layer spinning solution; Step 3, gained spinning liquid in step 1 and step 2 is placed in electrospinning device, the setting spinning head and receive plate distance as 15-20cm of electrospinning device, the flow velocity of stratum nucleare spinning liquid is 0.5-2.0m1/h, and stratum nucleare spinning liquid spinnerette diameters is 0.5-1.0mm; The flow velocity of shell layer spinning solution is 0.5-3.0ml/h, and shell layer spinning solution spinnerette diameters is 1.0-1.5mm; After stable outflow, applying electrostatic potential is 25kV, coaxial electrostatic spinning, collects and obtains non-woven fabric type fiber felt; Step 4, gained non-woven fabric type fiber felt in step 3 is calcined 11-15 hour under 500 DEG C of-1000 DEG C of conditions, obtain nuclear shell structure nano fiber.
Further, the mass ratio of butyl titanate, polyvinylpyrrolidone and ethanol is 1:1:50-60.
Further, the mass ratio of stannic chloride pentahydrate, Butter of antimony., polyvinylpyrrolidone and DMF is 30-40:20:5:40.
This high surface area nanofibers has the advantages that
(1) present invention adopts electrostatic spinning technique to prepare nucleocapsid structure (titanium dioxide stratum nucleare/tin-antiomony oxide shell) nanofiber, preparation method is simple, the nano-fiber material of gained, reduces the cost of conductive material, has great specific surface area.
(2) electrostatic spinning technique of the present invention is currently to prepare continuous, even the most simple and efficient long stapled method, and electrostatic spinning technique can prepare the diameter nano-scale fiber at 100-450nm. And electrostatic spinning technique has the advantages such as easy and simple to handle, low cost, has great development prospect and using value in preparing nanofiber.
Accompanying drawing explanation
Fig. 1: the electrospinning device structural representation used in the present invention.
Description of reference numerals:
1-stratum nucleare spinning liquid spinning head; 2-high voltage power supply; 3-shell layer spinning solution spinning head; 4-coaxial nozzle; 5-container; 6-collection device; 7-insulated enclosure lid; Axle transit passage in 8-; 9-side wall channels.
Detailed description of the invention
Below in conjunction with Fig. 1 and embodiment, the present invention will be further described:
As it is shown in figure 1, electrospinning device includes stratum nucleare spinning liquid spinning head 1, stratum nucleare spinning liquid spinning head 1 is arranged on one end of interior axle transit passage 9, and the other end of interior axle transit passage 9 is arranged in coaxial nozzle 4. Shell layer spinning solution spinning head 3 arranges on side wall channels 9, side wall channels 9 communicates with the sidewall of container 5, shell layer spinning solution passes sequentially through shell layer spinning solution spinning head 3 and side wall channels 9 enters in the coaxial nozzle 4 bottom container 5, and spray after mixing with stratum nucleare spinning liquid, the mixture of stratum nucleare spinning liquid and shell layer spinning solution is sprayed onto on collection device 6, collection device 6 is connected with the negative pole of high voltage power supply 2, and the positive pole of high voltage power supply 2 is connected with interior axle transit passage 9, goes back ground connection bottom collection device 6.
The electrostatic spinning process parameter that the present invention selects: the flow velocity of stratum nucleare spinning liquid is 0.5-2.0m1/h, and the flow velocity of shell layer spinning solution is 0.5-3.0m1/h. Flow velocity is excessive, and the droplet size that coaxial nozzle 4 place is not stretched in time is relatively big, solidifies due to solvent volatilization, can block coaxial nozzle 4, and flow velocity is too small, and fiber gathering speed is slow, and productivity is low.
Stratum nucleare spinning liquid spinnerette diameters is 0.5-1.0mm. Shell layer spinning solution spinnerette diameters is 1.0-1.5mm. Spinnerette diameters is too little, and polymer solution easily blocks, and spinnerette diameters is too big, it is easy to flows out and produces drippage. The setting spinning head and receive plate distance as 15-20cm of electrospinning device, receiving range is excessive, before fiber arrives collecting board, solvent fully volatilizees, fiber destroys pattern due to excessive tensile, accept apart from too small, after fiber arrives collecting board, owing to solvent does not fully volatilize, the solvent of residual is more, also can destroy the pattern of fiber.
Embodiment 1:
Step 1: measure 50 grams of ethanol, 1 gram of butyl titanate, 1 gram of polyvinylpyrrolidone are mixed and stirred in container, obtain homogeneous stratum nucleare spinning liquid.
Step 2: weigh 40g stannic chloride pentahydrate, 20g Butter of antimony., 5g polyvinylpyrrolidone are dissolved in 40gN, in dinethylformamide, obtain homogeneous shell layer spinning solution.
Step 3, gained spinning liquid in step 1 and step 2 is placed in electrospinning device, the setting spinning head and receive plate distance as 15-20cm of electrospinning device, the flow velocity of stratum nucleare spinning liquid is 0.5-2.0m1/h, and stratum nucleare spinning liquid spinnerette diameters is 0.5-1.0mm; The flow velocity of shell layer spinning solution is 0.5-3.0ml/h, and shell layer spinning solution spinnerette diameters is 1.0-1.5mm; After stable outflow, applying electrostatic potential is 25kV, coaxial electrostatic spinning, collects and obtains non-woven fabric type fiber felt.
Step 4, gained non-woven fabric type fiber felt in step 3 is placed in temperature programmed control Muffle furnace, 4 DEG C/min of heating rate, it is warming up to 700 DEG C, calcines 13h, obtain the nanofiber of nucleocapsid structure.
Embodiment 2:
Step 1: measure 60 grams of ethanol, 1 gram of butyl titanate, 1 gram of polyvinylpyrrolidone are mixed and stirred in container, obtain homogeneous stratum nucleare spinning liquid.
Step 2: weigh 30g stannic chloride pentahydrate, 20g Butter of antimony., 5g polyvinylpyrrolidone are dissolved in 40gN, in dinethylformamide, obtain homogeneous shell layer spinning solution.
Step 3, gained spinning liquid in step 1 and step 2 is placed in electrospinning device, the setting spinning head and receive plate distance as 15-20cm of electrospinning device, the flow velocity of stratum nucleare spinning liquid is 0.5-2.0m1/h, and stratum nucleare spinning liquid spinnerette diameters is 0.5-1.0mm; The flow velocity of shell layer spinning solution is 0.5-3.0m1/h, and shell layer spinning solution spinnerette diameters is 1.0-1.5mm; After stable outflow, applying electrostatic potential is 25kV, coaxial electrostatic spinning, collects and obtains non-woven fabric type fiber felt.
Step 4, gained non-woven fabric type fiber felt in step 3 is placed in temperature programmed control Muffle furnace, 4 DEG C/min of heating rate, it is warming up to 800 DEG C, calcines 11h, obtain the nanofiber of nucleocapsid structure.
Above in conjunction with accompanying drawing, the present invention is carried out exemplary description; the realization of the obvious present invention is not subject to the restrictions described above; as long as have employed the various improvement that the design of the method for the present invention carries out with technical scheme; or the not improved design by the present invention and technical scheme directly apply to other occasion, all in protection scope of the present invention.